Department of Chemistry, National Taiwan University, No. 1, Sec. 4, Roosevelt Road, Taipei, 10617, Taiwan.
J Am Chem Soc. 2020 Apr 15;142(15):7134-7144. doi: 10.1021/jacs.0c01482. Epub 2020 Mar 13.
Tetrafunctionalized calix[4]resorcinarene cavitands commonly serve as supramolecular scaffolds for construction of coordination-driven self-assembled capsules. However, due to the calix-like shape, the structural diversity of assemblies is mostly restricted to dimeric and hexameric capsules. Previously, we reported a spontaneous heteroleptic complexation strategy based on a pair of self-recognizable terpyridine-based ligands and Cd ions. Building on this complementary ligand pairing system, herein three types of nanocapsules, including a dimeric capsule, a Sierpiński triangular prism, and a cubic star, could be readily obtained through dynamic complexation reactions between a tetratopic cavitand-based ligand and various multitopic counterparts in the presence of Cd ions. The dimeric capsular assemblies display the spacer-length-dependent self-sorting behavior in a four-component system. Moreover, the precise multicomponent self-assembly of a Sierpiński triangular prism and a cubic star possessing three and six cavitand-based motifs, respectively, demonstrates that such self-assembly methodology is able to efficiently enhance architectural complexity for calix[4]resorcinarene-containing metallo-supramolecules.
四官能化杯[4]芳烃空腔受体通常作为超分子支架，用于构建配位驱动的自组装胶囊。然而，由于杯状形状，组装体的结构多样性主要限于二聚体和六聚体胶囊。此前，我们报道了一种基于一对自识别的三联吡啶基配体和 Cd 离子的自发杂配位络合策略。在此基础上，通过在 Cd 离子存在下，四齿空腔配体与各种多齿配体之间的动态络合反应，很容易得到三种纳米胶囊，包括二聚体胶囊、Sierpiński 三角棱柱和立方星。二聚体胶囊组装体在四组分体系中表现出间隔长度依赖性的自分类行为。此外，具有三个和六个空腔配体基元的 Sierpiński 三角棱柱和立方星的精确多组分自组装表明，这种自组装方法能够有效地提高含杯[4]芳烃金属超分子的结构复杂性。
